CN103328202B - DINT in foaming PVC paste - Google Patents

Abstract

The present invention relates to the foamable composite comprising at least one polymer, blowing agent and/or foam stabiliser and the terephthalic acid (TPA) dinonyl as plasticizer, described polymer is selected from polyvinyl chloride, polyvinylidene chloride, poly-vinyl butyrate, polyalkyl methacrylate and copolymer thereof, the average branchiness of the different nonyl of wherein said terephthalic acid (TPA) dinonyl 1.15 to 2.5 scope.The invention still further relates to and be foamed into shaped piece and the described foamable composite purposes for floor covering, wallpaper or artificial leather.

Description

DINT in foaming PVC paste

The present invention relates to foamable composite, it contains at least one polymer, blowing agent and/or foam stabiliser and the terephthalic acid (TPA) dinonyl as plasticizer, and described polymer is selected from polyvinyl chloride, polyvinylidene chloride, poly-vinyl butyrate, polyalkyl methacrylate and copolymer thereof especially.

Polyvinyl chloride (PVC) is one of most important polymer economically, and is used for multiple use as hard-PVC and soft-PVC.Important applied field is such as the frame of cable cover(ing), floor covering, wallpaper and plastic window.Plasticizer is added in PVC to improve elasticity.These Conventional plasticizers comprise such as phthalic acid ester, as di-2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP) and diisooctyl phthalate (DIDP).Nearest known cyclohexane cyclohexanedimethanodibasic ester as other plasticizer, such as naphthenic acid dinonyl (DINCH).

In many PVC product commonly, reduce product weight by applying froth bed and therefore reduce costs due to the use reducing material.For user, the product of foaming, such as, when floor covering, can bring the advantage of better impact sound insulation.

In preparation, foaming quality depends on many components, except the type of blowing agent and amount and except, PVC-type used and plasticizer also play an important role.Such as known, when use is easy to plasticizer (the so-called fast gelation agent) of gelling at least in proportion in filling a prescription, then especially can realize good foaming.

The known chain length along with ester increases, the dissolving/gelation temperature of this soft-PVC and therefore processing temperature rising.Its possible consequence is, because the variable color of PVC appears in this high temperature, is unacceptable in most applications.So-called fast gelation agent is added for reducing processing temperature.They also comprise such as Isononyl benzoate.But the shortcoming that due to the dissolving power that it is high, fast gelation agent has gradually (when at room temperature storing also) causes the viscosity of plastisol to significantly improve, therefore must add again thinner to compensate this effect.These measures are that cost is high and make process expensive.In addition known, in polymer plastisols/polymer paste, especially in many processing methods that PVC-plastisol/PVC-sticks with paste, processing speed especially depends on plastisol viscosity, and wherein low plastisol viscosity can realize higher processing speed and therefore improve the economy of production process.

Therefore a requirement in the manufacture of PVC-plastisol is in process, keep alap viscosity and low gelation temperature.In addition, the high storage stability of PVC-plastisol is also wish.

Almost the unknown not only significantly reduces the gelation temperature of preparation but also makes the viscosity of plastisol even after storage life a couple of days, also remain on low-level plasticizer so far.

EP1505104 describes containing the foamable composite of Isononyl benzoate as plasticizer.Use Isononyl benzoate to have remarkable shortcoming as plasticizer, namely Isononyl benzoate fairly volatilizees and therefore increases and overflow from polymer in process and with storage-and service time.This such as has very large shortcoming especially in indoor application.Therefore, in the prior art frequent using Isononyl benzoate as plasticizer filler and other conventional plasticizer, such as phthalic acid ester uses together.In addition, also Isononyl benzoate is used as fast gelation agent, wherein the agent of term fast gelation is used for realizing the plasticizer comparing (such as compared with terephthalic acid (TPA) dinonyl) gelling faster and/or gelling at lower temperatures.

Also known terephthaldehyde's acid alkyl ester is used in PVC as other plasticizer in the prior art.Such as, EP1808457A1 describes the use of dimethyl terephthalate ester, it is characterized in that, described alkyl residue there is the most Long carbon chain of at least 4 carbon atoms and the carbon atom of every alkyl residue add up to 5.It is said, the terephthalate in the most Long carbon chain of alcohol with 4 to 5 carbon atoms is suitable as the fast gelation plasticizer of PVC very much.It is said, this is surprising especially, because these terephthalate are considered to incompatible with PVC before this in the prior art.

Described bibliography is pointed out further, and dimethyl terephthalate ester also can be used in chemistry or mechanical foaming layer or is used in compacted zone or bottom.

WO2009/095126A1 describes mixture and the manufacture method thereof of the dinonyl of terephthalic acid (TPA).The feature of terephthalic acid (TPA) dinonyl mixture is the certain average branchiness of different nonyl residue in 1.0 to 2.2 scopes.This compound is used as the plasticizer of PVC.

Another shortcoming of prior art plasticizer is, when it is used in foamable composite, does not often reach enough foam heights when said composition foams.In order to obtain enough foam heights, then must use higher temperature, but cause yellow value degree to raise thus simultaneously and therefore cause the variable color of unacceptable PVC foam.Or, also can improve the amount of blowing agent in this formula or preparation, but this is very expensive for this reason.

Therefore technical purpose of the present invention is to provide foamable composite, and it has the less plasticizer of volatility and can realize at lower temperatures processing faster.

Described technical purpose is realized: at least one is selected from polyvinyl chloride by the foamable composite comprising following substances, polyvinylidene chloride, poly-vinyl butyrate, the polymer of polyalkyl methacrylate and copolymer thereof, a kind of blowing agent and/or foam stabiliser and the terephthalic acid (TPA) dinonyl as plasticizer, wherein the different nonyl of this ester average branchiness 1.15 to 2.5 scope, preferably 1.15 to 2.2 scope, more preferably 1.15 to 1.95 scope, scope particularly preferably in 1.25 to 1.85 and very particularly preferably 1.25 to 1.45 scope.

Have been found that the terephthalic acid (TPA) dinonyl containing having the fair average degree of branching can be processed when being manufactured foaming polymer composition by polyvinyl chloride or polyvinylidene chloride faster as the foamable composite of plasticizer in realization surprisingly.Find, compared with the plasticizer of prior art, owing to improving branching, achieve higher foam height with plasticizer required for protection, improve although stick with paste viscosity.This causes, and corresponding paste can be processed quickly, because they have demonstrated higher foam height in shorter time, and/or provides overall processing at lower temperatures.When this significantly improves/operational efficiency of sky-productive rate form or energy efficiency.

In addition find, although the paste viscosity of foamable composite of the present invention is more or less apparently higher than the paste viscosity using prior art plasticizer, but still higher foaming can be realized.This is astonishing, because higher paste viscosity also means " expansion resistance " of higher viscosity/higher usually, and therefore more can the less swelliong power of expectability.Higher foaming may, also owing to the less gelation rate of foamable composite of the present invention, although this is regarded as shortcoming in the prior art, be obvious advantage at this.This means, although gelation rate is obviously lower and stick with paste viscosity and improve compared with the foamable composite of prior art, can realize processing faster.

Sooner processing be important because thus can more low price ground and more efficiently manufacture a product.Such as, when processing plastisol, such as, when manufacturing wallpaper, floor covering and artificial leather, when applying material, corresponding machine can obviously run quickly, and boosts productivity thus.Especially in this case, when using terephthalic acid (TPA) dinonyl of the present invention, do not need or only need on a small scale additionally to use visbreaking material.

Another advantage is, this foamable composite can be processed at lower temperatures, and therefore also show obviously less yellow value degree (being caused by thermal decomposition), thus simultaneously, the yellow value degree of the composition, foam caused due to blowing agent (especially Celogen Az) and/or its incomplete decomposing diminishes.

In addition can determine, the volatility of terephthalic acid (TPA) dinonyl of the present invention is starkly lower than in prior art for the Isononyl benzoate in foamable composite.This is also beneficial to indoor application, because plasticizer volatility of the present invention is less and lessly overflow from plastics.

The method of the average branchiness of the different nonyl measuring terephthalic acid (TPA) dinonyl is described below.

The mensuration of the average branchiness of the different nonyl part in bis-terephthalate's mixture by ¹h-NMR method or ¹³c-NMR method is carried out.According to the present invention, preferably by ¹h-NMR spectral method at diisononyl esters at deuterochloroform (CDCl ₃) in solution in measure average branchiness.By 20 milligrams of substance dissolves at 0.6 milliliter of CDCl ₃in (comprising 1 quality %TMS) and by this solution load diameter be in the NMR pipe of 5 millimeters, record wave spectrum.The material studied and CDCl used ₃all first over a molecular sieve dry to get rid of in the value that records due to any error that the water that may exist causes.

Relative to for characterizing other method described in the such as WO03/029339 of alcohol residue, the method for this mensuration average branchiness is favourable, because water pollutions does not affect measurement result and their evaluation substantially.In principle, this NMR-Spectroscopy Study can be carried out with any commercially available NMR-equipment.This NMR-Spectroscopy Study uses the equipment from the model Avance500 of Bruker.Use at the temperature of 300K the delay of d1=5 second, 32 scanning, 9.7 microsecond pulse length and 10000Hz sweep width (spectral width), use 5mmBBO (broadbandobserver; Broadband is observed) probe record wave spectrum.Record resonance signal compared with the chemical shift as interior target tetramethylsilane (TMS=0ppm).By the comparable result of other commercially available NMR-equipment use same operation gain of parameter.The gained of the mixture of the dinonyl of terephthalic acid (TPA) ¹h-NMR spectrum extremely has in the scope of the minimum of a value of the lowest trough of 0.9 to 1.1ppm scope the resonance signal formed by the signal of the hydrogen atom of the methyl of different nonyl in fact at 0.5ppm.Substantially the hydrogen atom of the methylene adjacent with the oxygen of alcohol or alcohol residue is attributable at the signal of the chemical shift range of 3.6 to 4.4ppm.By measuring the area under each resonance signal, the area namely comprised between signal and baseline, quantizes.

Commercially available NMR-equipment has the device for integrated signal area.In this NMR-Spectroscopy Study, integration uses " xwinnmr " software, and version 3 .5 carries out.Then by 0.5ppm to the integrated value at the signal of the scope of the minimum of a value of the lowest trough of 0.9 to 1.1ppm scope divided by the integrated value of the signal in 3.6 to 4.4ppm scope, and obtain such intensity, this ratio gives the ratio of the number of hydrogen atoms existed in the adjacent methylene of number of hydrogen atoms and the oxygen atom existed in methyl.Have three hydrogen atoms due to every methyl and there are two hydrogen atoms in each methylene adjacent with oxygen atom, this intensity must respectively divided by 3 and 2 to obtain methyl number in different nonyl residue and the ratio adjacent to the methylene radix of oxygen atom.Due to the linear primary nonyl alcohol of the methylene that only has a methyl adjacent with oxygen atom with one containing side chain and therefore must not have 0 average branchiness, so must from this ratio subtracted amount 1.Therefore average branchiness V can be calculated according to following formula by the strength ratio recorded:

V=2/3*I(CH ₃)/I(OCH ₂)–1

Represent at this, the V=degree of branching, I (CH ₃)=area integral, it is attributed to methyl hydrogen atom substantially, and I (OCH ₂the area integral of the methylene hydrogen atom of)=adjacent with oxygen atom.

Composition of the present invention can containing being selected from following polymer: polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyacrylate, especially polymethyl methacrylate (PMMA), polyalkyl methacrylate (PAMA), fluoropolymer, especially polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), Pioloform, polyvinyl acetal, especially polyvinyl butyral resin (PVB), poly styrene polymer, especially polystyrene (PS), expandable polystyrene (EPS), acrylonitrile-styrene-acrylic ester copolymer (ASA), styrene-acrylonitrile (SAN), acrylonitrile-butadiene-styrene (ABS) (ABS), styrene-maleic anhydride copolymer (SMA), Styrene-methyl Acrylic Acid Copolymer, polyolefin, especially polyethylene (PE) or polypropylene (PP), TPO (TPO), polyethylene vinyl acetate (EVA), Merlon, PETG (PET), polybutylene terephthalate (PBT) (PBT), polyformaldehyde (POM), polyamide (PA), polyethylene glycol (PEG), polyurethane (PU), thermoplastic polyurethane (TPU), polysulfide (PSu), biopolymer, especially PLA (PLA), poly butyric (PHB), poly-hydroxypentanoic acid (PHV), polyester, starch, cellulose and cellulose derivative, especially NC Nitroncellulose (NC), ethyl cellulose (EC), cellulose acetate (CA), acetic acid/butyric acid-cellulose (CAB), the mixture of rubber or organosilicon and described polymer or monomer whose unit or copolymer.

Composition of the present invention preferably has PVC or based on following homopolymers or copolymer: the alkyl residue that ethene, propylene, butadiene, vinyl acetate, glycidyl acrylate, GMA, methacrylate, acrylate or have is bonded in side chain on the oxygen atom of ester group or straight chain alcohol is containing the acrylate of 1 to 10 carbon atom or methacrylate, styrene, acrylonitrile or cycloolefin.

In a preferred embodiment, this at least one polymer be contained in foamable composite is selected from polyvinyl chloride, polyvinylidene chloride, poly-vinyl butyrate, polyalkyl methacrylate and copolymer thereof.

In an especially preferred embodiment, this at least one polymer being contained in foamable composite is polyvinyl chloride (homopolymers or copolymer).

In one particularly preferred embodiment, this polymer can be vinyl chloride and the copolymer being selected from one or more following monomers: vinylidene chloride, vinyl acetate, propionate, vinyl butyrate, vinyl benzoate, methyl acrylate, ethyl acrylate or butyl acrylate.

In this foamable composite, the amount of terephthalic acid (TPA) dinonyl is advantageously every 100 mass parts polymer 5 to 120 mass parts, preferably 10 to 100 mass parts, particularly preferably 15 to 90 mass parts, and very particularly preferably 20 to 80 mass parts.

Optionally can in addition containing the other plasticizer except except terephthalic acid (TPA) dinonyl in this foamable composite, wherein said other plasticizer fused-and/or gelling ability can higher than, be equal to or less than terephthalic acid (TPA) dinonyl of the present invention.The mass ratio of other plasticizer used and terephthalic acid (TPA) dinonyl of the present invention used is in particular 1:10 to 10:1, preferred 1:10 to 8:1, particularly preferably 1:10 to 5:1, and especially preferred 1:10 to 1:1.

Ester, the ester of M-phthalic acid, the ester of terephthalic acid (TPA), the ester of cyclohexane cyclohexanedimethanodibasic, ester, the ester of citric acid, benzoic ester, the ester of different n-nonanoic acid, the ester of 2 ethyl hexanoic acid, the sad ester, 3 of trimellitic acid of described other plasticizer particularly phthalic acid, the ester of 5,5-tri-methyl hexanoic acid and/or be the ester of the ester of butanols, the ester of amylalcohol, the ester of octanol, the ester of 2-Ethylhexyl Alcohol, the ester of isononyl alcohol, the ester of decyl alcohol, the ester of dodecanol, the ester of tridecanol, the ester of glycerine and/or isobide and their derivative and mixture.

In addition preferably, foamable composite of the present invention contains blowing agent.This blowing agent can be the compound producing bubble, and it optionally uses together with so-called " facilitating agent ".Refer to that catalysis produces the component thermal decomposition of bubble and causes blowing agent to react generation bubble and make the catalyst of this foamable composition as facilitating agent.Blowing agent is also referred to as foaming agent.In principle, this foamable composite can chemistry (namely by blowing agent) or machinery (namely by introducing gas, preferred air) foaming.As producing the component (blowing agent) of bubble, resolve into gas componant under being preferably used in heat effect and said composition is expanded compound.

What be applicable to manufacture foam of polymers of the present invention comprises all types of known blowing agent for the blowing agent foamed, physics and/or CBA, comprises inorganic foaming agent and organic foaming agent.

The example of CBA is Celogen Az, azodiisobutyronitrile, benzene sulfonyl hydrazide, 4, 4-oxybenzene sulfonyl semicarbazide, 4, 4-oxo two (benzene sulfonyl hydrazide), diphenyl sulfone-3, 3-disulfonyl hydrazide, p-toluenesulfonyl semicarbazides, N, N-dimethyl-N, N-dinitrosoterephthalamine and three hydrazine triazines, N=N-dinitrosopentamethylene tetramine, dinitroso trimethyl triamine, sodium acid carbonate, sodium acid carbonate, the mixture of sodium acid carbonate and citric acid, ammonium carbonate, carbonic hydroammonium, saleratus, diazo aminobenzene, diazoaminotoluene, hydrazo-dicarbonamide, diazonium isobutyronitrile, Barium azodicarboxylate and 5-hydroxyl tetrazolium.

At least one of blowing agent used is particularly preferably Celogen Az, and it is release gaseous component when reacting, as N ₂, CO ₂and CO.The decomposition temperature of this blowing agent can be reduced by facilitating agent.

Mechanical foaming composition is also referred to as " whips (Schlagschaum) ".

In principle, foamable composite of the present invention can be such as plastisol.

Said composition preferably comprises suspension method-PVC, body-PVC, microsuspending method-PVC or emulsion-PVC in addition.Particularly preferably, at least one PVC polymer be contained in composition of the present invention is microsuspending method-PVC or emulsion-PVC.It is 60 to 90 that foamable composite of the present invention very particularly preferably has the molecular weight provided as K value (Fikentscher constant), and particularly preferably 65 to 85 emulsion-PVC.

This foamable composite preferably can comprise additive in addition, and it is selected from filler/reinforcing agent, pigment, delustering agent, heat stabilizer, antioxidant, UV stabilizing agent, co-stabilizer, solvent, viscosity modifier, foam stabiliser, fire retardant, tackifier and processing aid or process auxiliaries (such as lubricant) especially.

Heat stabilizer especially in and in PVC process and/or the hydrochloric acid dissociated afterwards suppress or postpone the thermal degradation of this polymer.All Common Polymers stabilizing agents of solid or liquid form, especially all common PVC-stabilizing agents all can be used as heat stabilizer, such as based on those of Ca/Zn, Ba/Zn, Pb, Sn or organic compound (OBS), the phyllosilicate combining acid also can be used, as hydrotalcite.Mixture of the present invention can have every 100 mass parts polymer 0.5 to 10, and preferably 1 to 5, the particularly preferably heat stabilizer content of 1.5 to 4 mass parts.

The so-called co-stabilizer, particularly epoxidized vegetable oil with plasticization can be used equally.Very particularly preferably use epoxidation linseed oil or epoxidised soybean oil.

Antioxidant normally suppresses by such as forming stable comple with the free radical generated the material that the free radical polyalcohol such as caused by energy emission is degraded targetedly.Especially comprise position resistance amine – so-called HALS stabilizing agent-, sterically hindered phenol, phosphite ester/salt, UV absorbent, such as hydroxy benzophenone ketone, hydroxy-phenyl benzotriazole class and/or arylamine.The antioxidant be applicable in composition of the present invention is also such as described in " HandbookofVinylFormulating " (editor: R.F.Grossman; J.Wiley & Sons; NewJersey (US) 2008) in.The content of antioxidant in expandable mixtures of the present invention is especially maximum 10 mass parts of every 100 mass parts polymer, preferably maximum 8 mass parts, particularly preferably maximum 6 mass parts, and particularly preferably 0.5 to 5 mass parts.

Within the scope of the present invention, inorganic pigment both can have been used also can to use organic pigment as pigment.Pigment content is especially every 100 mass parts polymer 0.01 to 10 mass parts, preferably 0.05 to 8 mass parts, particularly preferably 0.1 to 5 mass parts.The example of inorganic pigment is TiO ₂, CdS, CoO/Al ₂o ₃, Cr ₂o ₃.Known organic pigment is such as azo dyes, phthalocyanine color, triazine dioxin pigment, industrial carbon black (" Carbonblack ") and aniline pigment.Also special effect pigment can be used, such as, based on mica or based on those of synthetic vectors.

Viscosity modifier both can cause the general reduction (thinner or additive) of thickener-/plastisol viscosity also can change the curve that viscosity depends on shear rate (curve).Aliphatic series or aromatic hydrocarbon can be used as thinner, and carboxylic acid derivates, such as TXIB (Eastman company) known 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, or the mixture of carboxylate, such as, with the known wetting agent of product/trade name Byk, Viskobyk and Disperplast (BykChemie) and dispersant.Thinner is added: every 100 mass parts polymer 0.5 to 50, preferably 1 to 30, particularly preferably 2 to 10 mass parts with following ratio.

Mineral and/or synthesis and/or natural organic and/or inorganic material can be used as filler, such as calcium oxide, magnesia, calcium carbonate, barium sulfate, silica, phyllosilicate, industrial carbon black, pitch, timber (such as powdered, as particle, microparticle, fiber etc.), paper, natural-and/or synthetic fibers.Especially following material is preferably used to be used for composition of the present invention: calcium carbonate, silicate, talcum powder, kaolin, mica, feldspar, wollastonite, sulfate, industrial carbon black (so-called " carbon black ") and microballoon (particularly glass microsphere).At least one of filler used is especially particularly preferably calcium carbonate.Customary filler and the reinforcing agent of PVC-preparation are also such as described in " HandbookofVinylFormulating " (editor: R.F.Grossman; J.Wiley & Sons; NewJersey (US) 2008) in.Amount of filler used in composition of the present invention is especially maximum 150 mass parts of every 100 mass parts polymer, preferably maximum 120, particularly preferably maximum 100, and particularly preferably maximum 80 mass parts.In a specific embodiment, the toatl proportion of filler used in preparation of the present invention is maximum 90 mass parts of every 100 mass parts polymer, preferably maximum 80, particularly preferably maximum 70, and particularly preferably 1 to 60 mass parts.

As foam stabiliser, the commercially available foam stabiliser as mentioned in such as DE10026234C1 can be there is in the present compositions.This preferred foam stabiliser especially contains surface reactive material, the alkali metal-of such as aromatic sulfonic acid (such as alkyl benzene sulphonate) and/or alkali salt, and other aromatic compounds.Foam stabiliser can also based on organo-silicon compound and/or containing surfactant.Stabilizing agent based on soap/surfactant contain such as calcium dodecyl benzene sulfonate as active component.Based on organosilicon or based on soap foam stabiliser can such as at trade (brand) name Byk8020 and Byk8070(from BykChemie) under provide.Foam stabiliser with every 100 mass parts polymer 1 to 10 mass parts, preferably 1 to 8, and the amount of particularly preferably 2 to 4 mass parts uses.

This patent also provides this foamable composite for the purposes of floor covering, wallpaper or artificial leather.The present invention also provides the floor covering containing foamable composite of the present invention, the wallpaper containing foamable composite of the present invention or the artificial leather containing foamable composite of the present invention.

The terephthalic acid (TPA) dinonyl that average branchiness is 1.15 to 2.5 is manufactured according to the description in WO2009/095126A1.This ester exchange preferably by the mixture of the uncle's nonyl alcohol containing the terephthalate and isomery with the alkyl residue being less than 8 carbon atoms realizes.This manufacture is particularly preferably undertaken by the ester exchange of the mixture of uncle's nonyl alcohol of dimethyl terephthalate (DMT) and isomery.Or, also can manufacture terephthalic acid (TPA) dinonyl by terephthalic acid (TPA) to the esterification of mixture of uncle's nonyl alcohol with the corresponding above-mentioned degree of branching.

Commercially available material for the manufacture of terephthalic acid (TPA) dinonyl is such as special suitably from the nonanol mixture of EvonikOxeno company, it has 1.1 to 1.4 usually, the particularly average branchiness of 1.2 to 1.35, and from the nonanol mixture of ExxonMobil (Exxal9) company, it has the degree of branching of the highest 2.4.In addition, also can use the mixture of the nonyl alcohol of reduced branching degree, particularly there is the nonanol mixture of the degree of branching of maximum 1.5 and/or use available highly-branched nonyl alcohol, the such as nonanol mixture of 3,5,5-trimethyl hexanols on the market.In given boundary, average branchiness can be regulated targetedly by a rear way.

Terephthalic acid (TPA) ester in the ninth of the ten Heavenly Stems used in the present invention has following features in their thermal property (being measured by differential calorimetry/DSC):

1. they are at the first heating curves (initial temperature :-100 DEG C, the end temp :+200 DEG C of DSC Thermogram; The rate of heat addition: 10K/min.) in there is at least one glass transition point.

2. at least one glass transition point Di Yu – 70 DEG C detected in above-mentioned dsc measurement, preferably lower than-72 DEG C, particularly preferably lower than-75 DEG C, with particularly preferably lower than the temperature of-77 DEG C.In an advantageous embodiment, particularly when being intended to manufacture and there is plastisol or the foam of polymers of particularly preferred low-temperature flexibility, at least one glass transition point detected in above-mentioned dsc measurement is lower than-75 DEG C, preferably lower than-77 DEG C, particularly preferably lower than-80 DEG C, and particularly preferably lower than-82 DEG C.

3. they are at the first heating curves (initial temperature :-100 DEG C, the end temp :+200 DEG C of DSC Thermogram; The rate of heat addition: 10K/min.) in the melting signal (be 0J/g with therefore melting enthalpy) that do not have to detect.

Be used for the alkoxide component of esterification by selection or regulate glass transition temperature and melting enthalpy for the alcohol mixture of esterification.

Terephthalate used in the present invention shear viscosity at 20 DEG C is maximum 142mPa*s, preferred maximum 140mPa*s, particularly preferably maximum 138mPa*s, and particularly preferably maximum 136mPa*s.In an advantageous embodiment, particularly be intended to manufacture suitable examples as be exceedingly fast processing have especially low viscous plastisol time, terephthalate used in the present invention shear viscosity at 20 DEG C is maximum 120mPa*s, preferred maximum 110mPa*s, particularly preferably maximum 105mPa*s, and particularly preferably maximum 100mPa*s.Can by the shear viscosity using the isomeric nonanols for the manufacture of having of its specific (on average) degree of branching to regulate terephthalate of the present invention targetedly.

The present invention's mass loss of terephthalate at 200 DEG C after 10 minutes used is maximum 4 quality %, preferably maximum 3.5 quality %, particularly preferably maximum 3 quality %, and especially preferred maximum 2.9 quality %.In an advantageous embodiment, particularly when being intended to the foam of polymers manufacturing low emission, the present invention's mass loss of terephthalate at 200 DEG C after 10 minutes used is maximum 3 quality %, preferably maximum 2.8 quality %, particularly preferably maximum 2.6 quality %, and especially preferred maximum 2.5 quality %.By the selection of preparation composition, especially also can be affected targetedly by the selection of the terephthalic acid (TPA) dinonyl with the specific degree of branching and/or quality of regulation loss.

(liquid) density of the terephthalate that the present invention recorded by vibration U-pipe (Biegeschwinger) (at the temperature analyzing the purity of at least 99.7 area % and 20 DEG C according to GC) is used is at least 0.9685g/cm ³, preferably at least 0.9690g/cm ³, particularly preferably at least 0.9695g/cm ³, and especially preferred at least 0.9700g/cm ³.In a specific embodiment, (liquid) density of the terephthalate that the present invention recorded by vibration U-pipe (at the temperature analyzing the purity of at least 99.7 area % and 20 DEG C according to GC) is used is at least 0.9700g/cm ³, preferably at least 0.9710g/cm ³, particularly preferably at least 0.9720g/cm ³, and especially preferred at least 0.9730g/cm ³.Can by the density using the isomeric nonanols for the manufacture of having of its specific (on average) degree of branching to regulate terephthalate of the present invention targetedly.

Composition of the present invention can manufacture in every way.But, usually manufacture said composition by mixing all components strong in suitable mixer.Component is preferably added (also see " HandbookofVinylFormulating " (editor: R.F.Grossman at this in succession; J.Wiley & Sons; NewJersey (US) 2008)).

Foamable composite of the present invention can be used for the profiled member manufacturing foaming.Foamable composite of the present invention particularly preferably comprises at least one polymer being selected from polyvinyl chloride or polyvinylidene chloride or its copolymer.

Such as can mention artificial leather, floor or wallpaper as such foamed products, particularly preferably be the application of this foamed products in buffering-vinyl floor (CV floor) and wallpaper.

The foamed products be made up of foamable composite of the present invention is especially true to be manufactured, namely first this foamable composite is applied on carrier or another polymeric layer, and before application, or make afterwards said composition foam and final to apply and/or foaming composition impose hot-working (namely under heat energy effect, such as, by heating/heating).

Described foaming can machinery, physics or chemically carry out.The mechanical foaming of composition or plastisol is understood to mean plastisol and was such as introduced wherein (so-called " whips ") by air (or other gaseous matter) under abundant vigorous stirring before being applied on carrier, and this causes foaming.Usually need stabilizing agent for the stable foam formed thus.The foam structure of the foam that foam stabiliser major decision used is made, color and water absorbing capacity.The plasticizer that the selection of stabilizer types is also especially depended on.

Outside foam-expelling stabilizing agent, also can add other auxiliary agent with impact and/or additional stabilization foaming structure.At this in particular to dibenzoic acid diol ester.Dibenzoic acid diol ester is diethylene glycol dibenzoate (DEGDB), triethylene glycol dibenzoate (TEGDB) and dipropylene glycol dibenzoate (DPGDB) or its mixture mainly.

Except such as passing through except vigorous stirring mechanical foaming, foamable composite of the present invention can also use foamed gas physical blowing, under stress these gases and plastisol of the present invention are mixed in suitable commercial plant in this case, expand at low pressures subsequently.As physical blowing agent, inorganic and organic substance can be used.Suitable inorganic foaming agent comprises carbon dioxide, nitrogen, argon gas, water, air, oxygen and helium.

Organic foaming agent comprises the aliphatic hydrocarbon with 1 –, 6 carbon atoms, the aliphatic alcohol with 1 –, 3 carbon atoms and has the aliphatic hydrocarbon of halogenation wholly or in part of 1 –, 4 carbon atoms.Aliphatic hydrocarbon comprises methane, ethane, propane, normal butane, iso-butane, pentane, isopentane, neopentane, hexane, isohexane, heptane, octane, methylpentane, dimethyl pentane, butylene, amylene, 4-methylpentene, hexene, heptene, 2,2-dimethylbutanes and benzinum.Aliphatic alcohol comprises methyl alcohol, ethanol, normal propyl alcohol and isopropyl alcohol.The aliphatic hydrocarbon of halogenation comprises chloro-hydrocarbons, hydrofluorocarbons and chlorofluorocarbon wholly or in part.Chloromethanes, carrene, chloroethanes, dichloroethanes, 1,1,1-trichloroethanes, chloroform and tetrachloromethane is comprised for the chloro-hydrocarbons in the present invention.Fluoromethane, difluoromethane, fluoroethane, 1,1-Difluoroethane (HFC-152a), 1,1 is comprised for the hydrofluorocarbons in the present invention, 1-HFC-143a (HFC-143a), 1,1,1,2-HFC-134a (HFC-134a), 1,1,2,2 ,-HFC-134a (HFC-134), pentafluoroethane, 2,2-difluoropropane, 1,1,1-trifluoro propane and 1,1,1,3,3-pentafluoropropane.Chlorofluoromethane, dichlorodifluoromethane (HCFC-22), 1 is comprised for the partially hydrogenated chlorofluorocarbon in the present invention, 1-bis-chloro-1-fluoroethane (HCFC-141b), 1-chlorine-1,1-difluoroethane (HCFC-142b), 1,1-bis-chloro-2,2,2-HFC-143a (HCFC-123), 1,2-bis-chloro-1,2,2-HFC-143a (HCFC-123a) and 1-chloro-1,2,2,2-HFC-134a (HCFC-124).Also can use fully halogenated hydrocarbon, but due to ecological consideration not preferred: fluoro trichloromethane (CFC-11), dicholorodifluoromethane (CFC-12), 1,1, chloro-1,2, the 2-HFC-143a (CFC-113) of 2-tri-, 1,2-bis-chloro-1,1,2,2-HFC-134a (CFC-114), chloro-1,1,2,2,2-pentafluoroethane (CFC-115), Arcton 11.Especially, in the physical blowing using foamed gas, also use foam stabiliser and/or other auxiliary agent for affecting foaming structure.

When chemical blowing, the blowing agent of the gas componant that composition of the present invention to contain under heat effect completely or main decomposition becomes said composition is expanded.The decomposition temperature of this blowing agent significantly can be reduced by adding catalyst.These catalyst are well known to those skilled in the art as " facilitating agent " and can add as the system together with heat stabilizer individually or preferably.Composition of the present invention preferably containing at least one calcium-, zinc-or barium compound.Contrary with mechanical foam, can optionally omit use foam stabiliser when chemical blowing.

Be different from mechanical foam, when chemical blowing, add man-hour in (heat), usually in the gelling passage of heating, just form foam, wherein first the composition not yet foamed is applied on carrier, preferably by coating.In this embodiment of the method, dispensing solution can be pressed down by selective applying, such as, realize the shaping of foam by rotary screen printing equipment.Between processing period, be applied with on the position pressing down dispensing solution, or the expansion of plastisol do not occurring completely or only postpones to occur.In practice, use chemical blowing more obvious than mechanical foaming more.Further information about chemistry and mechanical foaming is found in such as " HandbookofVinylFormulating " (editor: R.F.Grossman, JohnWiley & SonsNewJersey (US) 2008) or technology textbook " PolymericFoamsandFoamTechnology " (D.Klempner, V.Sendijarevic; Hanser-Verlag; Munich; 2004).Optionally, also such as (further) die mould can be realized by means of knurling rolls by so-called machine printed subsequently.

In these two kinds of methods, can use and gained foam as carrier, such as textile web or nonwoven web keep those materials of good bond.But this carrier equally also can be only the temporary carrier that can remove again the made foam as froth bed from it.Such carrier can be such as bonding jumper or release liners (two-sided (Duplex)-paper).Another, the polymeric layer of optional (=pregelatinization) gelling wholly or in part also can serve as carrier.This especially implements when the CV floor be made up of multilayer.

In both cases, final hot-working is carried out in so-called gelling passage, usually carries out in an oven, is applied to the layer be made up of composition of the present invention on carrier through wherein, or is introduced in short time wherein by the carrier with this layer.This final hot-working is used for the solidification (gelling) of foaming layer.When chemical blowing, this gelling passage can be combined with the device for generation of foam.This such as can only use a gelling passage, wherein in its previous section, at a first temperature, chemical manufacture foam is carried out by making the decomposition of components of formation gas, and in the aft section of this gelling passage, preferred higher than at the second temperature of the first temperature, this foam is changed into semi-finished product or final products.

Passable in addition according to composition, at single temperature, carry out gelling and foaming simultaneously.Typical process temperature (gelation temperature) the scope of 130 to 280 DEG C, preferably the scope of 150 to 250 DEG C.This gelling is preferably so carried out, and this composition, foam is processed under above-mentioned gelation temperature and continues 0.2 to 5 minute, preferably continue 0.5 to 3 minute.When continuous process method, at this length by gelling passage and the speed adjustment heat treatment duration of carrier through this passage with this foam.Typical case's blowing temperature (chemical foam) is 160 to 240 DEG C, preferably 170 to 220 DEG C, especially preferably 180 to 215 DEG C.

When multilayer system, usually first making each layer fix its shape by carrying out so-called pregelatinization to applied plastisol at a temperature below foaming agent decomposition temperature, then can apply other layer (such as cover layer).If applied all layers, then carry out gelling-at a higher temperature and when chemical blowing, also foamed.Also shapingly cover layer can be transferred to by required by such method.

The advantage that foamable composite of the present invention has relative to prior art is, they can be processed at lower temperatures sooner, and therefore significantly improves the efficiency of the production process of PVC-foam.In addition, plasticizer volatility used in PVC foam is less, and therefore this PVC-foam is especially also specially adapted to indoor application.

Even without providing further details, those skilled in the art also can utilize above-mentioned explanation in scope the most widely.Therefore preferred embodiment and embodiment are only interpreted as descriptive and are in no case disclosing of being construed as limiting by any way.The present invention is explained in more detail below by means of embodiment.Alternate embodiment of the present invention can be obtained in a similar manner.

Embodiment:

Analyze:

1. the mensuration of purity

By means of GC, by the GC automatics " 6890N " of AgilentTechnologies, use the DB-5-post (length: 20m of J & WScientific, internal diameter: 0.25mm, film thickness 0.25 μm) and flame ionization detector, under following general condition, measure the purity of prepared ester:

Baking oven initial temperature: 150 DEG C of baking oven final temperatures: 350 DEG C

(1) firing rate 150-300 DEG C: 10K/min (2) isothermal: 10min at 300 DEG C

(3) firing rate 300-350 DEG C: 25K/min.

Total run time: 27min.

The inlet temperature of injection block: 300 DEG C of split ratio: 200:1

Partial flow rate: 121.1ml/min overall flow rate: 124.6ml/min.

Gas of carrier gas: helium Injection volume: 3 microlitres

Detector temperature: 350 DEG C of burning gases: hydrogen

Hydrogen flow rate: 40ml/min. air velocity: 440ml/min.

Make-up gas: helium make-up gas flow velocity: 45ml/min.

The evaluation of the gas chromatogram obtained relative to existing contrast material (phthalic acid two (different the ninth of the ten Heavenly Stems ester)/DINP, terephthalic acid (TPA) two (different the ninth of the ten Heavenly Stems ester)/DINT) to carry out by hand, purity represents with area percentage.Because the final content of target substance is up to >99.7%, so little by lacking the expected error of calibrating the respective sample material caused.

2. the mensuration of the degree of branching

The degree of branching of the ester prepared by measuring by NMR spectral method is carried out by means of the method described in detail above.

The mensuration of 3.APHA-color value

The color value of the ester made is measured according to DINENISO6271-2.

4. the mensuration of density

At 20 DEG C, measure the density of the ester made by vibration U-pipe according to DIN51757-method 4.

5. the mensuration of acid number

The acid number of the ester made is measured according to DINENISO2114.

6. the mensuration of water content

The water content of the ester made is measured according to DIN51777 part 1 (direct method).

7. the mensuration of inherent viscosity

Use the inherent viscosity (shear viscosity) being measured the ester made with the PhysicaMCR101 (Anton-Paar) of Z3 measuring system (DIN25mm) with rotary mode by following method:

First by ester and the measuring system temperature adjustment temperature at 20 DEG C, then by the following point of " Rheoplus " software control:

1. at 100s ^-1shear 60s in advance down, wherein do not record measured value (for eliminate the thixotropic effect that may occur and for improvement of Temperature Distribution).

2. frequency-lower line tilt, with 500s ^-1start and at 10s ^-1terminate, be divided into logarithmic series with 20 steps, the measurement point duration is respectively for 5s(checks Newtonian behavior).

All esters show Newtonian flow behavior.Such as at 42s ^-1shear rate under provide viscosity number.。

8. the mensuration of mass loss

The mass loss of ester at 200 DEG C of making is measured by Mettler halogen drying machine (HB43S).The measurement parameter be set as follows:

Temperature inclined-plane: constant 200 DEG C

Measured value record: 30s

Measuring Time: 10min

Sample size: 5g

This measurement uses disposable aluminium dish (Mettler company) and HS1 fabric filter (glass non-woven fabric from Mettler).At balance level-off with after taring, sample (5 grams) to be evenly distributed on fabric filter by disposable pipette and to start to measure.Twice mensuration is carried out and calculating mean value to each sample.Final measured value after 10 minutes is referred to as " mass losses at 200 DEG C after 10 minutes ".

9. carry out DSC-analytic approach, measure melting enthalpy

According to DIN51007(temperature range Cong – 100 DEG C to+200 DEG C) measure melting enthalpy and glass transition temperature by the first heating curves under the 10K/min rate of heat addition by differential calorimetry (DSC).Before measuring, by sample Leng Que Zhi – 100 DEG C in device for performing measurements, then with described heating rate.Measure under the nitrogen as protection gas.The flex point of heat flux curve is taken as glass transition temperature.With the integration determination melting enthalpy of the software in this equipment by peak area.

10. the mensuration of plastisol viscosity

The measurement PhysicaMCR101 (Anton-Paar company) of the viscosity of PVC-plastisol carries out, and wherein uses rotary mode and measuring system " Z3 " (DIN25mm).

First use spoon by this plastisol manual homogenizing in mixture container, inject described measuring system subsequently and at 25 DEG C of inferior temperature measurements.Following point is selected during measurement:

1. at 100s ^-1shearing 60s in advance down, wherein not recording measured value (for eliminating the thixotropic effect that may occur).

2. shear rate-lower line tilt, by 200s ^-1initial and at 0.1s ^-1terminate, be divided into logarithmic series with 30 steps, the measurement point duration is respectively 5s.

This measurement usual (unless otherwise specified) is carried out after this plastisol storage/slaking 24h.Before measurement, at this plastisol is stored in 25 DEG C.

The mensuration of 11. gelation rates

Plate-plate measuring system (PP25) that the research of the gelling behavior of plastisol controls running with oscillation mode shear stress in PhysicaMCR101 is carried out.This instrument is set up an extra heating mantles, to realize heat distribution as well as possible.

measurement parameter:

Pattern: thermograde (temperature inclined-plane)

Initial temperature: 25 DEG C

Final temperature: 180 DEG C

Heat/cool rates: 5K/min

Frequency of oscillation: 4 to 0.1Hz inclined-plane (logarithm)

Angular frequency: 101/s

The quantity of measurement point: 63

The measurement point duration: 0.5min

Automatic backlash adjusts: nothing

The constant measurement point duration

Gap width 0.5mm.

the enforcement of measuring:

With spoon, a plastisol to be measured is not applied in the lower plate of measuring system with having air bubble.It should be noted that after closing (zusammenfahren) with measuring system at this, part plastisol can be flowed out equably by this measuring system (around no more than about 6mm).Subsequently heating mantles to be placed on sample and to start to measure.

Measure the so-called complex viscosity that plastisol depends on temperature.The beginning of gelatinization identifies by sharply raising suddenly of complex viscosity.This viscosity raises and starts more early, then the gelling ability of this system is better.

By obtained experiment curv, determine that often kind of gel reaches the temperature of the complex viscosity of 1000Pa*s or 10000Pa*s by insertion.In addition, determine the maximum plastisol viscosity reached in this experimental provision by means of tangential method, and determine to occur the temperature of maximum plastisol viscosity from this temperature by drawing vertical line.

The manufacture of 12. foam paper tinsels and the mensuration of expansion rate

Be that the quick calibrator (KXL047 from Mitutoyo) of 0.01 millimeter measures foaming behavior by means of being applicable to the accuracy that has that soft-PVC measures.In order to manufacture paper tinsel, in the knife over roll (type: LTE-TS of MathisLabcoater; Manufacturer: W.MathisAG) scraper gap of upper setting 1 millimeter.And if this gap finger gauge inspection needs to regulate.By the knife over roll of MathisLabcoater by plastisol blade coating to the smooth release liners (WarranReleasePaper tightened in the frame; From SappiLtd.) on.In order to foaming percentage can be calculated, first manufactured under 200 DEG C/30 second time of staying and start gelling and the paper tinsel that not yet foams.Under the scraper gap condition provided, the thickness of described paper tinsel is 0.74 to 0.77 millimeter in all cases.Three diverse location detect thickness on paper tinsel.

Then same MathisLabcoater or manufacture foaming paper tinsel (foam) with 4 kinds of different stove time of staying (60s, 90s, 120s and 150s) wherein.After the foams were cooled, equally at three difference detect thickness.Need the mean value of thickness and original thickness to calculate to expand.(example: (depth of foam-original thickness)/original thickness * 100%=expands).

The mensuration of 13. yellow value degrees

Yellow value degree (index YD1925) is measuring of sample xanthochromia.When assess foam paper tinsel, yellow value degree is usually meaningful in two.On the one hand, which show the resolution (=yellow, in undecomposed state) of blowing agent Celogen Az, on the other hand, it is measuring (due to thermal stress variable color) of heat endurance.The SpectroGuide of the color measuring Byk-Gardner company of this foam paper tinsel carries out.Background as color measuring uses (commercial usual) white reference-ceramic tile.Setting following parameters:

Light source: C/2 °

Measure number: 3

Display: CIEL*a*b*

Measure index: YD1925

Measure these 3 diverse locations in sample to carry out (for special efficacy foam (Effektsch ume) and smooth foam (Glattsch ume) under 200 μm of plastisol blade thickness).On average derive from the value measured for 3 times.

embodiment 1:

The manufacture of terephthalate

1.1 by terephthalic acid (TPA) and the isononyl alcohol manufacture from EvonikOxenoGmbH terephthalic acid (TPA) dinonyl(DINT) (according to the present invention)

With separator and on set high in 4 liters of stirred flask of performance condenser, agitator, dipping tube, dropping funel and thermometer and load 644 grams of terephthalic acid (TPA)s (SigmaAldrichCo.), 1.59 grams of tetra-butyl orthotitanate (VertecTNBT in advance, JohnsonMattheyCatalysts) and 1440 grams of isononyl alcohols made by OCTOL method (EvonikOXENOGmbH), and by this mixture esterification to 240 DEG C.After 8.5 hours, reaction terminates.Then 190 DEG C and <1 millibar is distilled to, removing alcohol excess.Then this mixture be cooled to 80 DEG C and use the NaOH aqueous solution of 8 milliliter of 10 quality % to neutralize.Then under the pressure of the temperature of 180 DEG C and 20 to 5 millibars, steam distillation is carried out.Then this mixture is cooled to 130 DEG C and drying under 5 millibars at this temperature.After being cooled to <100 DEG C, filter this mixture through filter aid (perlite).Gained ester content (purity) is 99.9% according to GC.

1.2 by dimethyl terephthalate (DMT) (DMT) and the isononyl alcohol manufacture from EvonikOxenoGmbH to benzene two formic acid dinonyl(DINT) (according to the present invention)

In 4 liters of stirred flask with the band distillation bridge of reflux splitter, 20cmMultifill post, agitator, dipping tube, dropping funel and thermometer, loading 776 grams of dimethyl terephthalate (DMT)/DMT(Oxxynova in advance), initial 576 grams (EvonikOXENOGmbH) of 1.16 grams of tetra-butyl orthotitanates (VertecTNBT, JohnsonMattheyCatalysts) and 1440 grams of isononyl alcohols altogether.Under agitation slowly heat this mixture, until no longer solid can be seen.Continue heating until methyl alcohol appears in reflux splitter.Adjustment reflux splitter like this is held constant at about 65 DEG C to make column top temperature.From the bottom temp of about 240 DEG C, so slowly add remaining alcohol to make the temperature remained constant in flask and to keep enough backflows.Frequently study sample by GC and measure terephthalic acid (TPA) dinonyl content and terephthalic acid (TPA) methyl esters-different ester content in the ninth of the ten Heavenly Stems.At terephthalic acid (TPA) methyl esters-different ester content <0.2 area %(GC in the ninth of the ten Heavenly Stems) time, terminated diester exchange process.Be similar to the post processing described in embodiment 1.1 and carry out post processing.

1.3 by terephthalic acid (TPA) and the isononyl alcohol manufacture from ExxonMobil terephthalic acid (TPA) dinonyl(DINT) (according to the present invention)

With separator and on set high in 4 liters of stirred flask of performance condenser, agitator, dipping tube, dropping funel and thermometer and load 830 grams of terephthalic acid (TPA)s (SigmaAldrichCo.), 2.08 grams of tetra-butyl orthotitanate (VertecTNBT in advance, JohnsonMattheyCatalysts) and 1728 grams of isononyl alcohol (Exxal9 made according to Polygas method, and esterification at 245 DEG C ExxonMobilChemicals).After 10.5 hours, terminate reaction.Then by distilling under 180 DEG C and 3 millibars, removing alcohol excess.Then this mixture be cooled to 80 DEG C and use the NaOH aqueous solution of 12 milliliter of 10 quality % to neutralize.Then under the pressure of the temperature of 180 DEG C and 20 to 5 millibars, steam distillation is carried out.Then this mixture is dry under 5 millibars at this temperature, and after being cooled to <100 DEG C, filter.Gained ester content (purity) is 99.9% according to GC.

1.4 by terephthalic acid (TPA) and n-nonyl alcohol manufacture terephthalic acid (TPA) dinonyl(DINT) (comparative example)

Be similar to embodiment 1.1, replace isononyl alcohol and p phthalic acid esterification also post processing as mentioned above with n-nonyl alcohol (SigmaAldrichCo.).The product according to GC with >99.8% ester content (purity) becomes solid when being cooled to room temperature.

1.5 are manufactured by terephthalic acid (TPA) and 3,5,5-trimethyl hexanol terephthalic acid (TPA) dinonyl(DINT) (contrast example)

Be similar to embodiment 1.1, replace isononyl alcohol and p phthalic acid esterification also post processing as mentioned above with 3,5,5-trimethyl hexanol (OXEAGmbH).The product according to GC with >99.5% ester content (purity) becomes solid when being cooled to room temperature.

1.6 are manufactured by terephthalic acid (TPA), isononyl alcohol and 3,5,5-trimethyl hexanol terephthalic acid (TPA) dinonyl(DINT) (comparative example)

166 grams of terephthalic acid (TPA)s (SigmaAldrichCo.), 0.10 gram of tetra-butyl orthotitanate (VertecTNBT is loaded in advance in 2 liters of stirred flask of separator, high-performance condenser, agitator, dipping tube, dropping funel and thermometer, JohnsonMattheyCatalysts) isononyl alcohol (Exxal9 and by 207 grams made according to Polygas method, ExxonMobilChemicals) and 277 gram 3,5, the alcohol mixture that 5-trimethyl hexanol (OXEAGmbH) is made, and esterification to 240 DEG C.After 10.5 hours, terminate reaction.Then this stirred flask is connected on the Claisen bridge with vacuum distribution, and distillation is until 190 DEG C and <1 millibar, removing alcohol excess.Then this mixture be cooled to 80 DEG C and use the NaOH aqueous solution of 1 milliliter of 10 quality % to neutralize.Then by passing into nitrogen (so-called " air lift ") this mixture of purifying under the pressure of the temperature of 190 DEG C and <1 millibar.Then this mixture is cooled to 130 DEG C, and dry under <1 millibar at this temperature, and after being cooled to 100 DEG C, filter.Gained ester content (purity) is 99.98% according to GC.

1.7 are manufactured by terephthalic acid (TPA), isononyl alcohol and 3,5,5-trimethyl hexanol terephthalic acid (TPA) dinonyl(DINT) (according to the present invention)

166 grams of terephthalic acid (TPA)s (SigmaAldrichCo.), 0.10 gram of tetra-butyl orthotitanate (VertecTNBT is loaded in advance in 2 liters of stirred flask of separator, high-performance condenser, agitator, dipping tube, dropping funel and thermometer, JohnsonMattheyCatalysts) isononyl alcohol (Exxal9 and by 83 grams made according to Polygas method, ExxonMobilChemicals) and 153 gram 3,5, the alcohol mixture that 5-trimethyl hexanol (OXEAGmbH) is made, and esterification is until 240 DEG C.After 10.5 hours, terminate reaction.Then this stirred flask is connected on the Claisen bridge with vacuum distribution, and by being distilled to 190 DEG C and <1 millibar, removing alcohol excess.Then this mixture be cooled to 80 DEG C and use the NaOH aqueous solution of 1 milliliter of 10 quality % to neutralize.Then by passing into nitrogen (so-called " air lift ") this mixture of purifying under the pressure of the temperature of 190 DEG C and <1 millibar.Then this mixture is cooled to 130 DEG C, and dry under <1 millibar at this temperature, and after being cooled to 100 DEG C, filter.Gained ester content (purity) is 99.98% according to GC.

By the especially clear difference found out between the Isononyl benzoate for the manufacture of foam of polymers described in the prior (INB) and terephthalic acid (TPA) dinonyl used according to the invention of the significant difference of volatility (mass losses at 200 DEG C after 10 minutes).Here find, the value of high 20 times with regard to Isononyl benzoate.This high volatile volatile causes or only limitedly can not to use INB in many indoor application.

When use straight chain alcohol (n-nonyl alcohol; The degree of branching=0) manufacture terephthalate time, product as expected as be straight chain terephthalate.At room temperature, it is solid, and it can not be used in a conventional manner to manufacture plastisol.Even if at the highly-branched degree of about 3, as such as only used 3, when 5,5-trimethyl hexanol is as the highly-branched degree obtained during alkoxide component with p phthalic acid esterification, this terephthalate is at room temperature also solid and can not traditionally meaning processing again.If use isononyl alcohol and 3,5,5-trimethyl hexanol-mixture for the manufacture of terephthalate (see embodiment 1.6 and 1.7), then obtaining is at room temperature the product of solid or liquid according to average branchiness.In this case, this solidification process is usually delayed in time, be not namely after the cooling process or among start immediately, but only just to start after a few hours or a couple of days.。

There is no melting signal when measuring in DSC and show in its machinability, to be considered to best far below the ester of the glass transition of room temperature, because such as they can be stored in the outdoor tank do not heated in the world Anywhere at any season of the year, and can without difficulty through transport pump.In DSC Thermogram, not only show glass transition also show one or more melting signal, the ester namely showing partially crystallizable behavior no longer has machinability due to premature setting usually under European winter conditions (namely to the temperature of-20 DEG C).Whether according to this result, there is the degree of branching depending primarily on ester group in fusing point.If the degree of branching is lower than 2.5 but higher than 1, then obtain in DSC Thermogram, there is no melting signal and the ester being applicable to processing in the plastisol with ideal style.

embodiment 2:

Manufacture inflatable/can foaming PVC-plastisol (no-arbitrary pricing and/or pigment)

Below by the advantage of not adding filler, the PVC-plastisol of uncoloured heat-swellable illustrates plastisol of the present invention.Plastisol of the present invention is hereinafter in particular, for example for the manufacture of the plastisol of the heat-swellable of floor covering.Especially, following plastisol of the present invention is the froth bed being such as used as the back side foam in the PVC floor of sandwich construction.Preparation shown here is regarded as general, and those skilled in the art can maybe must make their adapt to the concrete processing-that is present in respective application and instructions for use.

Table 2: from the composition [all data are by mass parts] of the inflatable PVC-plastisol of embodiment 2

Plastisol formulation (embodiment 2)	1**	2*	3*	4*	5**	6**
							Vinnolit MP 6852	100	100	100	100	100	100
VESTINOL? 9	50
							According to terephthalic acid (TPA) two ester in the ninth of the ten Heavenly Stems of embodiment 1.1		50
According to terephthalic acid (TPA) two ester in the ninth of the ten Heavenly Stems of embodiment 1.3			50
							According to terephthalic acid (TPA) two ester in the ninth of the ten Heavenly Stems of embodiment 1.7				50
According to terephthalic acid (TPA) two ester in the ninth of the ten Heavenly Stems of embodiment 1.6					50
							VESTINOL? INB						50
Unifoam AZ Ultra 7043	3	3	3	3	3	3
							Zinc oxide	0.7	0.7	0.7	0.7	0.7	0.7

*=comparative example *=according to the present invention.

Be explained in more detail material therefor and material below:

VinnolitMP6852: having K value is that 68(is according to DINENISO1628-2) microsuspending method-PVC(homopolymers); From VinnolitGmbH & CoKG.

VESTINOL 9:(is adjacent) phthalic acid dinonyl (DINP), plasticizer; From EvonikOxenoGmbH.

VESTINOL INB: Isononyl benzoate, plasticizer; From EvonikOxenoGmbH.

UnifoamAZUltra7043: Celogen Az; Heat-activatable blowing agent; From HebronS.A.

Zinc oxide: ZnO; The decomposition catalyst of heat foamable agent; Reduce the intrinsic decomposition temperature of blowing agent; Also serve as stabilizing agent simultaneously; " Zinkoxidaktiv ^?"; From LanxessAG.By the plasticizer premix of the respective use of zinc oxide and enough (part), then add.

Liquid and solid formulation composition are weighed in PE-cup suitable separately respectively.Adjust spatula to stir so by hand this mixture ointment, to such an extent as to no longer include not wetting powder.The mixing Kreiss-dissolver VDKV30-3 (Niemann company of manufacturer) of this plastisol carries out.Mixing beaker is clamped in the clamping device of dissolver agitator.With mixing pan (fluted disc, serration, : 50mm) make sample homogenizing.At this, the rotating speed of dissolver is elevated to continuously the highest 2000 revs/min from 330 revs/min, and (due to frictional energy/energy dissipation, temperature improve until the temperature of temperature sensor numerical monitor arrives 30.0 DEG C to stir the so long time; See such as N.P.Cheremisinoff: " AnIntroductiontoPolymerRheologyandProcessing "; CRCPress; London; 1993).Guarantee the homogenizing realizing plastisol under the input of given energy thus.After this, by the temperature adjustment immediately of this plastisol to 25.0 DEG C.

embodiment 3:

Measure the plastisol viscosity of plastisol after 24 hour storage time (at 25 DEG C) of the heat-swellable made in embodiment 2

Using flow graph PhysicaMCR101 (Paar-Physica), as describing as analyzed in the 10th, measuring the viscosity of the plastisol made in embodiment 2.Result under shear rate 100/s, 10/s, 1/s and 0.1/s is exemplarily shown in following table (3).

Table 3: the plastisol from embodiment 2 stores the shear viscosity after 24 hours at 25 DEG C

According to the plastisol formulation of embodiment 2	1**	2*	3*	4*	5**	6**
							Shear viscosity [Pa*s] under shear rate=100/s	6.11	6.48	9.64	10.15	22.2	1
Shear viscosity [Pa*s] under shear rate=10/s	4.38	3.49	5.01	5.45	10.9	1.1
							Shear viscosity [Pa*s] under shear rate=1/s	4.95	3.37	4.3	4.55	8.23	2
Shear viscosity [Pa*s] under shear rate=0.1/s	7.74	4.68	5.62	5.91	11.3	5.1

*=comparative example *=according to the present invention.

Terephthalate used according to the invention produces to be had significantly lower paste viscosity and within the scope of high-rate of shear, is in the PC plastisol sticking with paste similar or slightly high level to comparable DINP compared with the plastisol based on current standard plasticizer DINP within the scope of low shear rate.Compared with the plastisol (6) based on Isononyl benzoate, at high shear rates, PVC-plastisol of the present invention has higher plastisol viscosity, and within the scope of low shear rate, realize identical or even lower viscosity number.Be very easy to find out the dependence of plastisol viscosity to the degree of branching of terephthalate used.The terephthalate with the ester group degree of branching of maximum 2.5 used according to the invention produces the plastisol with fabulous processing characteristics, and shows much higher shear viscosity based on the plastisol (5) that the comparative example 1.6 of more branching is obtained and common applying technology (such as blade coating) such as no longer can be used to process with having no problem.This INB-plastisol has pole low viscosity, and this is especially in the viscosity being also starkly lower than DINP-standard plastisol at high shear rates.Therefore, the inflatable plastisol at high shear rates with the machinability similar with similar DINP-plastisol is provided by terephthalate used according to the invention, but due to they lower plastisol viscosity at low shear rates, to show in such as spraying use obviously evenly flowing.

embodiment 4:

Measure the gelling behavior of the plastisol of the heat-swellable made in embodiment 2

As analyzed described in the 11st point (seeing above), after plastisol stores 24 hours at 25 DEG C, use PhysicaMCR101 with the gelling behavior of the plastisol of the heat-swellable made in oscillation mode testing example 2.Result is presented in following table (4).

Table 4: the characteristic point of the gelling behavior of the plastisol of the heat-swellable made according to embodiment 2 determined by gelling curve (viscograph)

Plastisol formulation (according to embodiment 2)	1**	2*	3*	4*	5**	6**
							Reach the temperature [DEG C] needed for plastisol viscosity of 1000 Pa*s	80	92.5	98	100	94	65
Reach the temperature [DEG C] needed for plastisol viscosity of 10 000 Pa*s	83.5	124	128	131	127.5	68
							Maximum plastisol viscosity [Pa*s]	45000	21100	17800	17200	18900	85300
Reach the temperature [DEG C] during maximum plastisol viscosity	116	139	142	141	142	82

*=comparative example *=according to the present invention.

The plastisol of heat-swellable of the present invention obviously has shortcoming compared with DINP plastisol (=standard plasticizer) in gelling property.Their on the one hand more slowly and/or gelling at a higher temperature, they only reach the half nearly (again at obviously higher temperature) of the final viscosity realized when comparable DINP plastisol on the other hand.According to common textbook suggestion (such as F.Xing, C.B.ParkinD.Klempner, V.Sendijarevic (editor); " PolymericFoamsandFoamTechnology "; Hanser; Munich; 2004; 9.3.2.9 chapter), therefore they should produce has higher foam density, i.e. the foam of more low bulk.Compared with DINP-standard plastisol and compared with terephthalate-plastisol of the present invention, INB-plastisol shows the gelling (or gelling at significantly lower temperature) be exceedingly fast, and has the peak viscosity apparently higher than DINP-standard in such cases.

embodiment 5:

Manufacture foam paper tinsel and the expansion-of the plastisol measuring the heat-swellable made in embodiment 2 at 200 DEG C or foaming behavior

Manufacture foam paper tinsel according to the method described under analysis the 12nd and measure expansion-/foaming behavior.Use the mean value of thickness and the initial thickness of 0.76 millimeter to calculate to expand.Result is presented in following table (5).

Table 5: the foam of polymers that (at 200 DEG C) are obtained by the plastisol (according to embodiment 2) of heat-swellable under the different stove time of staying in MathisLabcoater or the expansion of foam paper tinsel

Plastisol formulation (according to embodiment 2)	1**	2*	3*	4*	5**	6**
							Expansion [%] after 60s	42	35	62	49	22	8
Expansion [%] after 90s	400	386	393	385	420	326
							Expansion [%] after 120s	481	508	495	522	528	420

*=comparative example *=according to the present invention.

Compared with existing standard-plasticizer DINP, after 120 second time of staying, realized obviously higher foam height/expansion rate.Compared with DINP-standard sample and compared with plastisol of the present invention, corresponding INB-plastisol (plastisol formulation 6) all realizes significantly lower swell value in all cases.Although therefore provide gelling behavior significant adverse (see embodiment 4) but there is obvious advantage in heat-swellable and the plastisol of the heat-swellable therefore can processed sooner and/or process under more low processing temperature.

Also the decomposition completeness of blowing agent used and the process completeness of therefore expansion process can be found out by the color of the foam made.The yellow coloration of foam is less, and the progress extent of expansion process is higher.Yellow value degree according to the foam of polymers made in the embodiment 5 that analysis the 13rd point (seeing above) records or foam paper tinsel is presented in following table (6).

Table 6: the yellow value degree (Y of the foam of polymers made in embodiment 5 _id1925)

Plastisol formulation (according to embodiment 2)	1**	2*	3*	4*	5**	6**
							Yellow value degree [%] after 60s	57	59.5	58.5	58.8	61.8	67.9
Yellow value degree [%] after 90s	29	32.6	29.4	33.1	31.5	31.2
							Yellow value degree [%] after 120s	21	20	21	19.3	18.5	18.1

*=comparative example *=according to the present invention.

Although the inflatable plastisol containing terephthalate according to the present invention after 90 second time of staying is also more or less apparently higher than comparable DINP-foam in yellow value degree, after 120 seconds, they also reach more or less significantly lower level.INB-plastisol from obviously higher level, when 90 second time of staying still higher than DINP-standard, and to terminate with the comparable level of plastisol made based on terephthalate used according to the invention.Therefore also confirm here, compared with existing standard plasticizer DINP, terephthalate used according to the invention and the plastisol with its heat-swellable of the present invention made can obviously be processed quickly.

embodiment 6:

Manufacture inflatable/can foaming PVC-plastisol (use filler and pigment)

Be intended to the advantage that plastisol of the present invention is described by means of the PVC-plastisol of the heat-swellable containing filler and pigment below.Under the plastisol of the present invention that shows at this in particular, for example for the manufacture of the plastisol of the heat-swellable of floor covering.Especially, the plastisol of the present invention shown under is such as can to print in the PVC-floor being used as sandwich construction and/or can the froth bed of (inhibierbare) upper foam of resistance.

But, with the formula changed, manufacture plastisol similar to Example 2ly.The amount of being weighed into of the component of used various plastisols can be learned from following table (7):

Table 7: according to the interpolation filler of embodiment 6 and the composition [all data are by mass parts] of painted inflatable PVC-plastisol

Plastisol formulation (embodiment 6)	1**	2*	3*	4*	5**	6**
							Vinnolit MP 6852	60	60	60	60	60	60
VESTINOL? 9	45
							According to terephthalic acid (TPA) two ester in the ninth of the ten Heavenly Stems of embodiment 1.1		45
According to terephthalic acid (TPA) two ester in the ninth of the ten Heavenly Stems of embodiment 1.3			45
							According to terephthalic acid (TPA) two ester in the ninth of the ten Heavenly Stems of embodiment 1.7				45
According to terephthalic acid (TPA) two ester in the ninth of the ten Heavenly Stems of embodiment 1.6					45
							Isononyl benzoate						45 18 -->
Calibrite – OG	60	60	60	60	60	60
							KRONOS 2220	4	4	4	4	4	4
Isopropyl alcohol	2	2	2	2	2	2
							Unifoam AZ Ultra 7043	1.5	1.5	1.5	1.5	1.5	1.5
Zinc oxide	0.85	0.85	0.85	0.85	0.85	0.85

*=comparative example *=according to the present invention.

The material therefor do not occurred in explained later previous embodiment and material:

Calibrite-OG: calcium carbonate; Filler; From OMYAAG.

KRONOS2220: with the rutile pigment (TiO that Al and Si is stable ₂); Chinese white; From KronosWorldwideInc.

Isopropyl alcohol: the cosolvent for reducing plastisol viscosity and the additive for improvement of foaming structure (from BrenntagAG).

embodiment 7:

Measure the plastisol viscosity of plastisol after 24 hour storage life (at 25 DEG C) through adding filler and painted heat-swellable from embodiment 6

Use flow graph PhysicaMCR101(from Paar-Physica) viscosity of plastisol as made in measurement embodiment 6 as described in analyzing under the 10th point (seeing above).In following table (8), indication example is as the result under shear rate 100/s, 10/s, 1/s and 0.1/s.

Table 8: the plastisol from embodiment 6 stores the shear viscosity after 24 hours at 25 DEG C

According to the plastisol formulation of embodiment 6	1**	2*	3*	4*	5**	6**
							Shear viscosity [Pa*s] under shear rate=100/s	6.5	6.7	9	8.9	n.bb.	1
Shear viscosity [Pa*s] under shear rate=10/s	7	6.6	8.6	9.3	n.bb.	1.3
							Shear viscosity [Pa*s] under shear rate=1/s	10.6	8.9	11.1	12.8	306	2.4
Shear viscosity [Pa*s] under shear rate=0.1/s	21	16.4	20.2	24.4	529	6.9

*=comparative example *=according to the present invention.

Based on the plastisol (comparative example of Isononyl benzoate (INB); Plastisol formulation 6) under all shear rates illustrated, there is minimum shear viscosity.Compared with being used as the DINP of standard plasticizer, plastisol of the present invention has more or less significantly lower shear viscosity, and this causes the working properties obviously improved, and especially causes the rate of application significantly improved when coating and/or blade coating.The impact of branching on plastisol viscosity is apparent.Have the degree of branching be 2.8 as sample 5(comparative sample) sample measured shown the viscosity of a magnitude higher than other sample at low shear rates, under more high-rate of shear, owing to exceeding measurement tolerance, must stop to measure.Therefore this confirm, such plastisol cannot be processed.On the contrary, the invention provides the plastisol according to the selected degree of branching with the working properties similar with the plastisol based on standard plasticizer DINP or the obvious working properties improved.

embodiment 8:

Measure the gelling behavior of the plastisol through adding filler and painted heat-swellable from embodiment 6

As analyzed described in the 11st point (seeing above), after plastisol is stored 24 hours at 25 DEG C, use PhysicaMCR101 with the gelling behavior of the plastisol through adding filler and painted heat-swellable obtained in oscillation mode research performation example 6.Result is presented in following table (9).

Table 9: the characteristic point of the gelling behavior determined by the gelling curve (viscograph) through adding filler and painted inflatable plastisol obtained according to embodiment 6

Plastisol formulation (according to embodiment 6)	1**	2*	3*	4*	5**	6**
							Reach the temperature [DEG C] needed for plastisol viscosity of 1000 Pa*s	82	113	117	118	118	67
Reach the temperature [DEG C] needed for plastisol viscosity of 10 000 Pa*s	100	135	138	139	140	71
							Maximum plastisol viscosity [Pa*s]	31 300	16 400	14 900	13 900	13 700	45 200
Reach the temperature [DEG C] during maximum plastisol viscosity	132	144	147	146	147	111

*=comparative example *=according to the present invention.

As do not added the plastisol of heat-swellable of filler (see embodiment 4; Table 4) illustrated general, the plastisol made based on Isononyl benzoate (INB) has the fastest gelling and/or minimum gelation temperature in all plastisols illustrated.Can find out as when not adding the plastisol of filler equally, when the plastisol containing filler, between DINP-plastisol (=standard) and the plastisol containing terephthalic acid (TPA) ester in the ninth of the ten Heavenly Stems, showing the significant difference of gelling behavior.When terephthalate, gelling is carried out comparatively slow and is just started at obviously higher temperature.In addition, the only about half of height of DINP-plastisol is only by the accessible maximum plastisol viscosity of gelling.Therefore here also because the foaming behavior of the plastisol containing terephthalic acid (TPA) ester in the ninth of the ten Heavenly Stems is obviously not as DINP-plastisol.

embodiment 9:

The expansion-of the plastisol of heat-swellable manufacturing foam paper tinsel and measure preparation in embodiment 6 at 200 DEG C or foaming behavior

Manufacture foam paper tinsel similarly with the method described under analysis the 12nd and measure expansion behavior, but in use embodiment 6, preparation through adding filler and painted plastisol.Result is presented in following table (10).

Table 10: the foam of polymers that (at 200 DEG C) are obtained by the plastisol (according to embodiment 6) through adding filler and painted heat-swellable under the different stove time of staying in MathisLabcoater or the expansion of foam paper tinsel

Plastisol formulation (according to embodiment 6)	1**	2*	3*	4*	5**	6**
							Expansion [%] after 60s	0	0	5	0	20	8
Expansion [%] after 90s	230	190	250	192	300	224
							Expansion [%] after 120s	285	300	315	300	360	184

*=comparative example *=according to the present invention.

As expected, expand when containing Packed plastisol and be starkly lower than packless those (see embodiments 5).But, as when packless plastisol, after 120 second time of staying, realized again obvious higher foam height with the plastisol containing terephthalate used according to the invention compared with existing standard-plasticizer.In contrast, the time of staying that the plastisol formulation (6) based on Isononyl benzoate (INB) only arrives maximum 90 seconds just has the level that is in DINP-standard (1) but lower than the expansion of the obtainable value of thickener according to the present invention (3), shrinks again subsequently.With DINP-standard with compared with the plastisol based on terephthalate used according to the invention, INB-final sample (after 120 seconds) has obviously lower and complete not satisfied expansion.Based on the comparative sample (5) of the terephthalic acid (TPA) dinonyl of highly-branched although have fabulous expandable, be not suitable for commercial Application due to its extremely disadvantageous rheological behaviour (see table 8).Therefore the plastisol of the Packed heat-swellable of tool is provided, although its significant adverse (see embodiment 8) in gelling behavior has obviously favourable heat-swellable.

Also (although there is Chinese white) completeness of the decomposition of blowing agent Celogen Az used and the completeness of therefore expansion process can be found out by the color of prepared foam when the Packed plastisol of tool.The xanthochromia of foam is less, and the completeness of expansion process is higher.

As the foam of polymers of preparation in the embodiment 9 that records according to analysis the 13rd point (seeing above) or the yellow value degree of foam paper tinsel are presented in following table (11).

Table 11: according to the yellow value degree (Y of foam of polymers prepared by embodiment 9 _id1925)

Plastisol formulation (according to embodiment 6)	1**	2*	3*	4*	5**	6**
							Yellow value degree [%] after 60s	22.8	23.1	23.2	22.7	23.5	23.9
Yellow value degree [%] after 90s	19.5	20	19.2	19.2	18.2	17.6
							Yellow value degree [%] after 120s	19.1	16.7	18.9	15.9	14.5	16.1

The plastisol prepared based on Isononyl benzoate (INB) starts with the highest yellow value degree of the plastisol of all measurements, but is down to the level of plastisol of the present invention after 120 second time of staying at 200 DEG C.After 90 seconds, the plastisol containing terephthalate used according to the invention has just been in the level of DINP-plastisol.After 120 seconds, obtain significantly lower value in the situation than DINP, namely expansion process is carried out obviously faster.Therefore provide tool Packed plastisol, although its significant adverse when gelling allows process velocity and/or lower processing temperature faster.

embodiment 10:

Manufacture be used for special efficacy foam through add filler and painted inflatable/can foaming PVC-plastisol

Be intended to the advantage that plastisol of the present invention is described by means of the PVC-plastisol containing the heat-swellable of filler and pigment being suitable for manufacturing special efficacy foam (there is the foam of special surface structure) hereinafter.According to from the known performance pattern of field of textiles, these foams are also often referred to as " chinchilla (Boucle)-foam ".Under show that plastisol of the present invention is at this plastisol of heat-swellable in particular, for example for using when manufacturing wall coverings.Especially, show under that plastisol of the present invention is such as the froth bed used in PVC wallpaper.

Manufacture plastisol similar to Example 2ly but with through change formula.The amount of being weighed into of the component of used various plastisols can be learned from following table (12):

Table 12: from the composition [all data are by mass parts] through adding filler and painted inflatable PVC-plastisol of embodiment 10

Plastisol formulation	1**	2*	3*	4*	5*	6**
							Vestolit E 7012 S	25	25	25	25	25	25
Vinnolit E 67 ST	15	15	15	15	15	15
							Vinnolit EP 7060	10	10	10	10	10	10
VESTINOL? 9	25
							According to terephthalic acid (TPA) two ester in the ninth of the ten Heavenly Stems of embodiment 1.1		20
According to terephthalic acid (TPA) two ester in the ninth of the ten Heavenly Stems of embodiment 1.7			20
							According to terephthalic acid (TPA) two ester in the ninth of the ten Heavenly Stems of embodiment 1.6				20
According to terephthalic acid (TPA) two ester in the ninth of the ten Heavenly Stems of embodiment 1.3					20
							Eastman DBT		5	5	5	5	25
Unicell D200A	2.25	2.25	2.25	2.25	2.25	2.25
							Tracel OBSH 160NER	0.5	0.5	0.5	0.5	0.5	0.5 21 -->
Kronos 2220	1.5	1.5	1.5	1.5	1.5	1.5
							Microdol A1	15.5	15.5	15.5	15.5	15.5	15.5
Baerostab KK 48-1	1.25	1.25	1.25	1.25	1.25	1.25
							Isopropyl alcohol	1.5	1.5	1.5	1.5	1.5	1.5

*=comparative example *=according to the present invention.

The material used not yet provided in previous embodiment and material describe in detail hereinafter:

VestolitE7012S: there is K value and record according to DINENISO1628-2 for 67() emulsion-PVC(homopolymers); From VestolitGmbH.

VinnolitE67ST: there is K value and record according to DINENISO1628-2 for 67() emulsion-PVC(homopolymers); From VinnolitGmbH & Co.KG.

VinnolitEP7060: there is K value and record according to DINENISO1628-2 for 70() emulsion-PVC(homopolymers); From VinnolitGmbH & Co.KG.

EastmanDBT: di-n-butyl terephthalate; There is the plasticizer of fast gelation effect; From EastmanChemicalCo.

UnicellD200A: Celogen Az; Heat-activatable blowing agent; From TramacoGmbH.

TracelOBSH160NER: subtract quick sulfohydrazide (OBSH); Heat-activatable blowing agent; From TramacoGmbH.

MicrodolA1: miemite (dolomite); Filler; From OmyaAG.

BaerostabKK48-1: potassium/zinc-" facilitating agent "; The decomposition catalyst of heat foamable agent; Reduce the intrinsic decomposition temperature of blowing agent; Also there is stabilization simultaneously; From BaerlocherGmbH.

embodiment 11:

Measure the plastisol viscosity of plastisol after 24 hour storage life (at 25 DEG C) through adding filler and painted heat-swellable from embodiment 10

Use flow graph PhysicaMCR101(from Paar-Physica), as the viscosity of plastisol made in measurement embodiment 10 as described in analyzing under the 10th point (seeing above).The exemplary result be presented under shear rate 100/s, 10/s, 1/s and 0.1/s in following table (13).

Table 13: the plastisol from embodiment 10 stores the shear viscosity after 24 hours at 25 DEG C

According to the plastisol formulation of embodiment 10	1**	2*	3*	4**	5*	6**
							Shear viscosity [Pa*s] under shear rate=100/s	9.15	7.2	8.15	14.5	8.15	n.bb.
Shear viscosity [Pa*s] under shear rate=10/s	10.7	6.75	7.1	12	7.5	49
							Shear viscosity [Pa*s] under shear rate=1/s	16.6	9.7	9.6	16.7	10	146
Shear viscosity [Pa*s] under shear rate=0.1/s	34.8	20	18.2	33.9	19.4	655

*=comparative example *=can not record according to n.bb.=of the present invention.

Use the dibutyl terephthalate (EastmanDBT) of fast gelation to produce the plasticizer (at room temperature may pregelatinization) with extra high viscosity as sole plasticiser, this obviously can not use traditional technology method to process.Compared to the plastisol (1) only based on DINP, the plastisol of the present invention of the dibutyl terephthalate containing terephthalic acid (TPA) dinonyl mixture and small scale has significantly lower viscosity, and it is also starkly lower than the viscosity of terephthalic acid (TPA) ester admixture in the different ninth of the ten Heavenly Stems (4) of the highly-branched of non-invention.Therefore the present invention provides the plastisol allowing obviously to process sooner compared with known standard (DINP).

embodiment 12:

Measure the gelling behavior of the plastisol through adding filler and painted heat-swellable from embodiment 10

As described in analyzing under the 11st point (seeing above), after plastisol stores 24 hours at 25 DEG C, use PhysicaMCR101 with the gelling behavior of the plastisol through adding filler and painted heat-swellable of preparation in oscillation mode research performation example 10.Result is presented in following table (14).

Table 14: the characteristic point of the gelling behavior determined by the gelling curve (viscograph) through adding filler and painted inflatable plastisol prepared according to embodiment 10

Plastisol formulation (according to embodiment 10)	1**	2*	3*	4**	5*	6**
							Reach the temperature [DEG C] needed for plastisol viscosity of 1000 Pa*s	74	76	79	79	79	54
Reach the temperature [DEG C] needed for plastisol viscosity of 10 000 Pa*s	84	96	100	101	101	61
							Maximum plastisol viscosity [Pa*s]	25200	21000	20000	20700	19900	98500
Reach the temperature [DEG C] during maximum plastisol viscosity	117	125	127	127	127	78

*=comparative example *=according to the present invention.

Also the specific position of dibutyl terephthalate base plastisol obviously can be identified in gelling curve.It at room temperature starts under the level of other plastisols all considered apparently higher than (about 2 times), and this shows at room temperature just pregelatinization and machinability deficiency.About incipient gelation temperature, plastisol of the present invention is in the level of standard-plastisol (DINP) equally, attainable maximum final viscosity is also like this, and the speed that just plastisol of the present invention reaches maximum plastisol viscosity from incipient gelation temperature is slightly slower than DINP-plastisol.Therefore the plastisol manufacturing special efficacy foam is provided for, its processing characteristics (see embodiment 11) in improvement-there is the gelling property substantially similar with current standard system, and simultaneously not containing phthalic acid ester.

embodiment 13:

Manufacture and evaluate the special efficacy foam of the plastisol through adding filler and painted heat-swellable derived from according to embodiment 10

After the storage time of about 2 hours, make the plastisol of preparation in embodiment 10 at MathisLabcoater(type LTE-TS; Manufacturer: W.MathisAG) middle foaming.The wallpaper (from AhlstromGmbH) through coating is used as carrier.Scraper coating device is used to apply plastisol with 3 kinds of different-thickness (300 microns, 200 microns and 100 microns).Successively 3 kinds of plastisols are applied on paper respectively.By foaming and the gelling 60 seconds at 210 DEG C in Mathis baking oven of the paper through precoating that so obtains.

On the sample of complete gelation, yellow value degree is measured as described in analyzing under the 13rd point (seeing above).

In the evaluation of expansion behavior, use DINP-sample standard as a comparison.Standard expansion behavior (=" O.K. ") therefore corresponds to the behavior of DINP-sample.When so-called " foam overblow ", foaming structure is caved in, and namely there is poor expansion behavior here.

In the evaluation of surface quality or surface texture, special uniformity or the systematicness evaluating surface texture.The size of each effect part enters evaluation equally.

Another is evaluated is oozing out or moving the evaluation back side (paper) with regard to formula components.The rating system of surface texture evaluation is presented in following table (15).

Table 15: for evaluating the evaluation system of the surface quality of special efficacy foam

evaluate	implication
		1	fabulous surface texture (the high systematicness of surface effect and uniformity; The size of each effect is suitable for).
2	excellent surface structure (the high systematicness of surface effect and uniformity; The size of each effect is suitable for).
		3	(systematicness of surface effect and uniformity can accept satisfied surface texture; The size of each effect is suitable).
4	surface texture is passed (slightly irregular or inconsistent in surface texture; The size of each effect is slightly unbalance).
		5	defective surface texture is (irregular and inconsistent in surface texture; The size of each effect is unbalance).
6	not enough surface texture (very irregular and inconsistent surface texture; The size of each effect is not suitable for (much bigger/much smaller)).

The back side is evaluated based on the evaluation of (migration) rating system in following table (16).

Table 16: the evaluation system of the back side evaluation of special efficacy foam

evaluate	implication
		1	fabulous (do not have discernible diffusion or migration; Aberration is not had) in edge region.
2	good (do not have discernible diffusion or migration; Minimum aberration in edge region).
		3	satisfied (few discernible diffusion or migration; Slight color differences in applying region).
4	qualifying (slight discernible diffusion or migration; Obvious aberration in applying region).
		5	defectiveness (clearly moves sign; Slightly " greasy " sense of touch; Remarkable aberration in whole applying region).
6	deficiency (moves sign significantly; Significantly " greasy " sense of touch; Extreme aberration in whole applying region).

The surface texture of special efficacy foam (namely should have the foam of special/especially obvious surface structuration) determines mainly through the composition of plastisol that uses for the manufacture of it and processing characteristics.Especially can mention the gelling behavior (especially the size of bubble and distribution being played a decisive role) of the flow behavior (such as characterizing with the process of the plastisol viscosity equation as shear rate) of plastisol viscosity, plastisol, plastisol at this, plasticizer used decomposes the impact of (so-called " Auto-Kick-effect ") and the selection of one or more blowing agents and one or more decomposition catalysts and combination to blowing agent.These substantially affect by the selection of material therefor and can be controlled targetedly thus.

Evaluate and can infer plasticizer used and the persistence of other formula components in this complete gelation system through the back side of Tu Fu paper.Except optics and aesthetic shortcoming and except, the remarkable migration of formula components also has many real drawbacks.Such as, because the viscosity improved causes adhering to the dust that cannot remove or cannot remove completely again, and therefore in very short time, disadvantageous outward appearance is caused.In addition, the migration of formula components has very adverse influence to the printability of printed matter or persistence usually.In addition, the not controlled release of wall coverings can be caused with the interaction of fixed adhesive (such as Wall paper adhesive).

What surface-and the back side were evaluated the results are summarized in table 17.

Table 17: the result that surface-and the back side from the complete gelation special efficacy foam of embodiment 13 are evaluated

Plastisol formulation (according to embodiment 10)	1**	2*	3*	4**	5*	6**
							Expansion behavior	-	O.K.	O.K.	O.K.	O.K.	Foam overblow
Yellow value degree	7.3	6.6	6.7	6.5	6.8	6.3
							The evaluation of surface quality/-structure	2	1	1	1	1	6
The back side after 24 hours is evaluated	1	1	1	1	1	1
							The back side after 7 days is evaluated	1	2	2	1	2	1

*=comparative example *=according to the present invention.

Except only containing dibutyl terephthalate (DBT) as the sample of plasticizer expansion behavior and except, the expansion behavior of all samples is all good, and is equal to DINP-standard.DBT is very easy to foam overblow, namely has poor expansion behavior.Yellow value degree shows, compared with DINP-standard, realizes significantly lower value when plastisol of the present invention, and meaning expands carries out obviously faster at this.The result of the expansion behavior of the evaluation display DBT-plastisol of surface texture.Because foam overblow causes forming not enough surface texture and/or causing it to cave in too early.On the contrary, all plastisols of the present invention show fabulous surface texture, and they show obvious improvement even surprisingly compared with DINP-standard.With regard to the transport phenomena of obviously (namely visually), all samples none stored (at 25 DEG C) at 24 hours after show any migration sign.Even stored after (at 25 DEG C) at 7 days, all special efficacy foams of the present invention none show any transport phenomena.The present invention be therefore provided in visual aspects be better than or be at least equal to known prior art and have in machinability thus remarkable advantage plastisol and can special efficacy foam prepared therefrom.

embodiment 14:

Manufacture be used for level and smooth foam through add filler and painted inflatable/can foaming PVC-plastisol

Be intended to the advantage that plastisol of the present invention is described by means of the PVC-plastisol containing the heat-swellable of filler and pigment being suitable for manufacturing so-called level and smooth foam (there is the foam of smooth surface) hereinafter.At this, under the plastisol of heat-swellable that in particular, for example uses when manufacturing wall coverings of the plastisol of the present invention that shows.Especially, show under that plastisol of the present invention is such as froth bed used in PVC-wallpaper.

Similar to Example 2ly, but use through change formula manufacture plastisol.Can learn from following table (18) for various plastisol use the amount of being weighed into of component.

Table 18: from the composition [all data are by mass parts] through adding filler and painted inflatable PVC-plastisol of embodiment 14

Plastisol formulation	1**	2*	3*	4**	5*	6**
							Vestolit E 7012 S	20	20	20	20	20	20
Vinnolit E 67 ST	17.5	17.5	17.5	17.5	17.5	17.5
							Vestolit B 6021 Ultra	12.5	12.5	12.5	12.5	12.5	12.5
VESTINOL? 9	30
							According to terephthalic acid (TPA) two ester in the ninth of the ten Heavenly Stems of embodiment 1.1		25
According to terephthalic acid (TPA) two ester in the ninth of the ten Heavenly Stems of embodiment 1.7			25
							According to terephthalic acid (TPA) two ester in the ninth of the ten Heavenly Stems of embodiment 1.6				25
According to terephthalic acid (TPA) two ester in the ninth of the ten Heavenly Stems of embodiment 1.3					25
							Eastman DBT		5	5	5	5	30
Unicell D200A	1.8	1.8	1.8	1.8	1.8	1.8
							Drapex 39	2.4	2.4	2.4	2.4	2.4	2.4
Kronos 2220	2.4	2.4	2.4	2.4	2.4	2.4
							Microdol 1	24	24	24	24	24	24
Baerostab KK 48-1	1	1	1	1	1	1

*=comparative example *=according to the present invention.

The material used not yet provided in previous embodiment and material describe in detail hereinafter:

VestolitB6021Ultra: there is K value and measure according to DINENISO1628-2 for 60() microsuspending method-PVC(homopolymers); From VestolitGmbH.

Drapex39: epoxidised soybean oil; There is (being total to) stabilizing agent of plasticization; From Chemtura/Galata.

embodiment 15:

Measure the plastisol viscosity of plastisol after 24 hour storage life (at 25 DEG C) through adding filler and painted heat-swellable from embodiment 14

Use flow graph PhysicaMCR101(from Paar-Physica), as measured the viscosity of the plastisol made in embodiment 14 as described in analyzing under the 10th point (seeing above).The result such as under shear rate 100/s, 10/s, 1/s and 0.1/s is shown in following table (19).

Table 19: the plastisol from embodiment 14 stores the shear viscosity after 24 hours at 25 DEG C

According to the plastisol formulation of embodiment 14	1**	2*	3*	4**	5*	6**
							Shear viscosity [Pa*s] under shear rate=100/s	8.2	6.9	8.2	n.bb.	8.3	10.9
Shear viscosity [Pa*s] under shear rate=10/s	7.4	5.4	7	23.7	6.95	16.2
							Shear viscosity [Pa*s] under shear rate=1/s	8.4	5.8	7.2	23.7	6.8	29
Shear viscosity [Pa*s] under shear rate=0.1/s	13	8.9	11.2	35.2	10.2	75

*=comparative example *=can not record according to n.bb.=of the present invention.

With pure DINP(=standard) compared with and compared with pure terephthalic acid (PTA) dibutyl ester, with good grounds embodiments of the invention show significantly lower plastisol viscosity.More the comparative example (4) of highly-branched has obviously higher plastisol viscosity equally, and when high-rate of shear, as it is such as to exist by blade coating or spray process, both immeasurability also can not be processed.Therefore provide and allow the obviously better plastisol with processing sooner relative to current standard.

embodiment 16:

Measure the gelling behavior of the plastisol through adding filler and painted heat-swellable from embodiment 14

As analyzing described in the 11st point (seeing above), after plastisol stores 24 hours at 25 DEG C, use PhysicaMCR101 with the gelling behavior of the plastisol through adding filler and painted heat-swellable of preparation in oscillation mode research performation example 14.Result is presented in following table (20).

Table 20: the characteristic point of the gelling behavior determined by the gelling curve (viscograph) through adding filler and painted dilatant plastisol prepared according to embodiment 14

Plastisol formulation (according to embodiment 14)	1**	2*	3*	4**	5*	6**
							Reach the temperature [DEG C] needed for plastisol viscosity of 1000 Pa*s	81	89	93	94	93	62
Reach the temperature [DEG C] needed for plastisol viscosity of 10 000 Pa*s	98	120	123	123	122	66
							Maximum plastisol viscosity [Pa*s]	22700	16000	14100	14200	14700	73700
Reach the temperature [DEG C] during maximum plastisol viscosity	125	132	132	132	134	80

*=comparative example *=according to the present invention.

As mentioned when special efficacy foam formulation (see embodiment 12), the plastisol based on pure terephthalic acid (PTA) dibutyl ester has at room temperature shown obvious pregelatinization sign.Therefore, although fast gelation at low temperatures, not there is the machinability using conventional art.Although plastisol of the present invention has the slightly slow gelling under the gelation temperature slightly improved, when being issued to the maximum paste viscosity in gelatinized with similar temperature when DINP-standard plastisol.Therefore provide plastisol, its when significantly improved processing characteristics (see embodiment 15)-there is the gelling property substantially similar with current standard system, and simultaneously not containing phthalic acid ester.

embodiment 17:

Manufacture and evaluate the level and smooth foam of the plastisol of the heat-swellable derived from according to embodiment 14

Manufacture level and smooth foam similarly with the method described in embodiment 13, but use the plastisol made in embodiment 14.Expansion behavior is evaluated similarly with the method described in embodiment 13.On the sample of complete gelation, yellow value degree is measured as described in analyzing under the 13rd point (seeing above).When evaluating surface quality or the surface texture of level and smooth foam, evaluate emphatically uniformity and/or the slickness of surface texture.In addition, with regard to formula components ooze out/move evaluate the back side (paper).Evaluation system is presented in following table (21).

Table 21: the evaluation system of the surface quality of level and smooth foam

Evaluate	Implication
		1	Fabulous surface texture (high uniformity & flatness; Without scrambling)
2	Good surface texture (high uniformity & flatness; Few scrambling)
		3	(uniformity & flatness can accept gratifying surface texture; Few scrambling)
4	Surface texture (the flatness that the slight inconsistent & in surface texture reduces of passing; Obvious but equally distributed scrambling)
		5	Defective surface texture (the flatness that the obvious inconsistent & in surface texture obviously reduces; Obvious discernible scrambling)
6	Not enough surface texture (significantly inconsistent surface texture, the surface of obviously coarse and/or granular sensation and/or fluctuating, the remarkable uneven distribution of scrambling)

The back side is evaluated similarly with the evaluation (see embodiment 13/ table 16) when special efficacy foam.

As when special efficacy foam, mainly through determining the surface texture of level and smooth foam (namely should have the foam of smooth surface texture) for the manufacture of the processing characteristics of its plastisol.Especially can mention that again the gelling behavior (especially playing a decisive role on the size of bubble and distribution) of the flow behavior (such as characterizing with the process of the plastisol viscosity equation as shear rate) of plastisol viscosity, plastisol, plastisol, bubble coalescence speed and plasticizer used decompose the impact of (so-called " Auto-Kick-effect ") to blowing agent at this, and the selection of one or more blowing agents and one or more decomposition catalysts and combination.In addition percent opening or rate of closed hole by using surface reactive material (such as dispersant and or wetting agent) to control this foam targetedly.Therefore in this case, raw-material selection also has material impact to final result.

Evaluate and can infer again plasticizer used and the persistence of other formula components in complete gelation system through the back side of Tu Fu paper.The remarkable transport of formula components has many shortcomings as already discussed and " culling level " of the use of normally corresponding formula.

Surface assessment result is summarised in following table (22).

Table 22: the result that surface-and the back side from the complete gelation special efficacy foam of embodiment 14 are evaluated

Plastisol formulation (according to embodiment 14)	1**	2*	3*	4**	5*	6**
							Expansion behavior	-	O.K.	O.K.	O.K.	O.K.	O.K.
Yellow value degree	8.8	8.2	8.5	8.4	8.4	8.7
							The evaluation of surface quality/structure	2	2	2.5	2.5	2	2
The back side after 24 hours is evaluated	1	1	1	1	1	1
							The back side after 7 days is evaluated	1	2	2	2	2	1

With good grounds embodiments of the invention all show with the comparable expansion behavior of DINP-standard and bar none lower than the yellow value degree of the value of DINP-standard.The surface quality of the level and smooth foam made is suitable with DINP-standard-level and smooth foam, does not observe the migration in wallpaper equally.Therefore the plastisol and foam compared with known prior art with the character obviously improved are provided.

Claims (8)

1. realize the method for more high-foaming, it is characterized in that using in foamable composite the average branchiness of different nonyl 1.15 to 2.5 the terephthalic acid (TPA) dinonyl of scope as plasticizer;

Wherein said foamable composite also comprises the polymer that at least one is selected from polyvinyl chloride, poly-vinyl butyrate, polyhydroxyalkanoatefrom, polyalkyl methacrylate, polyvinylidene chloride and copolymer thereof, also comprises blowing agent and/or foam stabiliser; Described blowing agent is CBA.

2. method according to claim 1, is characterized in that, described polymer is polyvinyl chloride.

3. method according to claim 1, it is characterized in that, described polymer is vinyl chloride and the copolymer being selected from one or more following monomers: vinylidene chloride, vinyl acetate, propionate, vinyl butyrate, vinyl benzoate, methyl acrylate, ethyl acrylate or butyl acrylate.

4. according to the method for any one of claims 1 to 3, it is characterized in that, the amount of terephthalic acid (TPA) dinonyl is every 100 mass parts polymer 5 to 120 mass parts.

5. according to the method for any one of claims 1 to 3, it is characterized in that, in described foamable composite, comprise the other plasticizer beyond terephthalic acid (TPA) dinonyl in addition.

6. according to the method for any one of claims 1 to 3, it is characterized in that, described foamable composite contains the component producing bubble facilitates agent as blowing agent and optional foaming.

7. according to the method for any one of claims 1 to 3, it is characterized in that, described foamable composite contains microsuspending method-PVC and/or emulsion-PVC.

8. according to the method for any one of claims 1 to 3, it is characterized in that, described foamable composite contains and is selected from other following composition: filler, pigment, delustering agent, heat stabilizer, co-stabilizer, antioxidant, viscosity modifier, foam stabiliser, processing aid and lubricant.